JP6611777B2 - Lubricant composition comprising an acyclic hindered amine - Google Patents

Description

  The present invention relates generally to lubricant compositions. More particularly, the present invention relates to a lubricant composition comprising an acyclic amine compound, a method of forming the lubricant composition, and an additive concentrate of the lubricant composition.

  It is known and customary to add stabilizers to lubricant compositions based on mineral or synthetic oils in order to improve their performance characteristics. Antioxidants are a particularly important stabilizer. Oxidative degradation of the lubricant composition plays an important role in the combustion chamber of the engine due to the presence of oxides of nitrogen that catalyze the oxidation of the lubricant composition.

  Several conventional amine compounds are effective stabilizers for lubricants. These conventional amine compounds can help neutralize the acid formed during the combustion process. However, these conventional amine compounds are generally not used in internal combustion engines due to their adverse effects on fluoroelastomer seals.

  An object of the present invention is to provide a lubricant composition comprising a base oil and an acyclic amine compound.

（式中、Ｒ^１はそれぞれ独立して水素及び１〜１７個の炭素原子を有するアルキル基から選択され、Ｒ^１のうち少なくとも２つは独立して選択されたアルキル基であり、
Ｒ^２はそれぞれ独立してアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有し、
Ｒ^３は水素及びアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有する）
を有する。 The present invention provides a lubricant composition comprising a base oil and an acyclic amine compound. The acyclic amine compound has the following formula (I):

Wherein each R ¹ is independently selected from hydrogen and an alkyl group having 1 to 17 carbon atoms, at least two of R ¹ are independently selected alkyl groups;
Each R ² is independently selected from an alcohol group, an alkyl group, an amide group, an ether group, and an ester group, each having 1 to 17 carbon atoms;
R ³ is selected from hydrogen and alcohol groups, alkyl groups, amide groups, ether groups, and ester groups, each having 1 to 17 carbon atoms)
Have

  The present invention describes the stabilization of lubricant compositions with certain types of amine compounds, acyclic amine compounds. Lubricant compositions containing these amine compounds help neutralize the acid formed during the combustion process.

DETAILED DESCRIPTION OF THE INVENTION One aspect of a lubricant composition is the amount of basic material dispersed / dissolved therein, which is referred to as the total base number (“TBN”) of the lubricant composition. TBN is an industry standard measurement used to correlate the basicity of any material with the basicity of potassium hydroxide. This value is measured by two ASTM titration methods, ASTM D2896 and ASTM D4739. Most TBN comes from the use of overbased metal soaps, but these soaps have created some new engine technology problems such as diesel particulate filters. Formulations that minimize the use of these metal soaps are valuable and are called “low SAPS oils” (SAPS stands for sulfated ash, phosphorus and sulfur).

  The low SAPS designation requirement inherently limits the amount of conventional calcium and magnesium based detergents found in lubricant compositions. These conventional detergents had many functions, including the neutralization of acids formed during the combustion process and resulting from the oxidation of the base oil in the lubricant composition. However, limiting the amount of these conventional calcium and magnesium detergents that can be included has reduced the ability of the lubricant composition to neutralize the acid. As a result of the reduced ability of the lubricant composition to neutralize the acid, it became necessary to change the lubricant composition more frequently.

  The present invention provides a lubricant composition comprising a base oil and an acyclic amine compound. The present invention also provides a method of forming a lubricant composition and a method of lubricating a system with the lubricant composition. Furthermore, the present invention provides an additive concentrate for a lubricant composition comprising an acyclic amine compound. Lubricant compositions and their methods are further described below. Acyclic amine compounds are useful for adjusting the total base number (TBN) of the lubricant composition. Acyclic amine compounds are also useful for other purposes as described below.

を有する。式（Ｉ）中、Ｒ^１はそれぞれ独立して水素及び１〜１７個の炭素原子を有するアルキル基から選択され、ここでＲ^１のうち少なくとも２つは独立して選択されたアルキル基である。あるいは、Ｒ^１はそれぞれ独立して１〜１２個、１〜１０個、１〜８個、又は１〜６個の炭素原子を有するアルキル基から選択され得る。Ｒ^１によって表されるそれぞれのアルキル基は直鎖状又は分枝鎖状であってよい。式（Ｉ）中、Ｒ^２はそれぞれ独立してアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有する。Ｒ^２はそれぞれ独立して１〜１５個、１〜１２個、１〜８個、１〜６個、又は１〜４個の炭素原子を有してよい。Ｒ^２によって表されるそれぞれの基は、直鎖状又は分枝鎖状であってよい。Ｒ^３は、水素及びアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有する。あるいは、Ｒ^３はそれぞれ、１〜１０個、１〜８個、１〜６個、又は１〜４個の炭素原子を有してよい。Ｒ^３によって表されるそれぞれの基は、直鎖状又は分枝鎖状であってよい。 The acyclic amine compound has the following formula (I):

Have In formula (I), each R ¹ is independently selected from hydrogen and an alkyl group having 1 to 17 carbon atoms, wherein at least two of R ¹ are independently selected alkyl groups. . Alternatively, each R ¹ can be independently selected from alkyl groups having 1 to 12, 1 to 10, 1 to 8, or 1 to 6 carbon atoms. Each alkyl group represented by R ¹ may be linear or branched. In formula (I), each R ² is independently selected from an alcohol group, an alkyl group, an amide group, an ether group, and an ester group, each having 1 to 17 carbon atoms. R ² may each independently have 1 to 15, 1 to 12, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Each group represented by R ² may be linear or branched. R ³ is selected from hydrogen and alcohol groups, alkyl groups, amide groups, ether groups, and ester groups and each has 1 to 17 carbon atoms. Alternatively, each R ³ may have 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Each group represented by R ³ may be linear or branched.

At least two groups represented by R ¹ are each independently selected alkyl groups. Alternatively, at least three or exactly four groups represented by R ¹ of the acyclic amine compound are independently selected alkyl groups.

In certain embodiments, at least one group represented by R ¹ , R ² and R ³ is unsubstituted. Alternatively, at least 2, 3, 4, 5, or 6 groups represented by R ¹ , R ² and R ³ are unsubstituted. For “unsubstituted”, the represented group does not include pendant functional groups such as hydroxyl, carboxyl, oxide, thio, and thiol groups, and the represented group is such as oxygen, sulfur, and nitrogen heteroatoms. It is intended not to include acyclic heteroatoms. In other embodiments, the groups represented by R ¹ , R ^2, and R ³ are all unsubstituted. Alternatively, it is conceivable that one, two, three, four, five or six groups represented by R ¹ , R ² and R ³ are substituted. The term “substituted” means that the group represented comprises at least one pendant functional group such as hydroxyl, carboxyl, oxide, thio, thiol group, and combinations thereof, or the group represented , Oxygen, sulfur, nitrogen, and combinations thereof, including at least one acyclic heteroatom.

Exemplary R ¹ , R ² , and R ³ groups are methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl. , N-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl groups.

  The amine compound is acyclic. The term “acyclic” is intended to mean that the amine compound does not contain any cyclic structure.

  In one or more embodiments, the acyclic amine compound has a weight average molecular weight in the range of 100-1200. Alternatively, the acyclic amine compound has a weight average molecular weight in the range of 200 to 800, or 200 to 600. The mass average molecular weight of the acyclic amine compound can be measured by a plurality of known techniques such as gel permeation chromatography.

  In one or more embodiments, the acyclic amine compound is non-polymeric. The term “non-polymeric” means the fact that an acyclic amine compound contains less than 50, 40, 30, 20, or 10 monomer units.

  In one or more embodiments, the acyclic amine compound does not contain phosphorus. Alternatively, it is conceivable that the acyclic amine compound consists of nitrogen, hydrogen, and carbon atoms. Alternatively, it is also conceivable that the acyclic amine compound consists of nitrogen, hydrogen, oxygen and carbon atoms. Furthermore, it is also conceivable that the acyclic amine compound does not form a salt or complex with other components in the lubricant composition.

を含む群から選択される。 In one particular embodiment, the acyclic amine compound comprises the following compound:

Selected from the group comprising

  Acyclic amine compounds are used in the lubricant composition in amounts ranging from 0.1 to 10% by weight to form the lubricant composition. Alternatively, the acyclic amine compound is used in the lubricant composition in an amount ranging from 0.5 to 5% by weight, or from 1 to 3% by weight, based on the total weight of the lubricant composition.

  Alternatively, when the lubricant composition is formulated as an additive concentrate, the amine compound is 0.5-90% by weight, 1-50% by weight, 1-30, based on the total weight of the additive concentrate. It may be included in an amount ranging from 5% by weight or from 5 to 25% by weight.

  The conventional use of conventional amine compounds has included the formation of reaction products of such conventional amine compounds with various acids, oxides, triazoles, and other reactive components. In these applications, the conventional amine compound is consumed by a particular reaction, so the final formed lubricant composition does not contain a significant amount of the conventional amine compound. In such conventional applications, over 50% by weight of conventional amine compounds, based on the total weight of conventional amine compounds, typically reacts with various acids in the lubricant composition. In contrast, the lubricant composition of the present invention and the method of the present invention contain a significant amount of an acyclic amine compound in an unreacted state. The term “unreacted” refers to the fact that the unreacted portion of the acyclic amine compound does not react with any component in the lubricant composition. Thus, the unreacted portion of the acyclic amine compound remains unused if the lubricant composition is present in the lubricant composition before it is used in an end user application such as an internal combustion engine.

  In certain embodiments, at least 90% by weight of the acyclic amine based on the total weight of the acyclic amine compound utilized to form the lubricant composition prior to reaction in the lubricant composition. The compound remains unreacted in the lubricant composition. Alternatively, at least 95 wt%, 96 wt%, 97 wt%, 98 wt% or 99 wt% acyclic amine compound based on the total weight of the acyclic amine compound prior to reaction in the lubricant composition Remains unreacted in the lubricant composition.

  The phrase “before reaction in the lubricant composition” refers to a measure of the amount of acyclic amine compound in the lubricant composition. This phrase does not require the acyclic amine compound to react with other components in the lubricant composition, i.e., the total mass of the acyclic amine compound prior to reaction in the lubricant composition. 100% by weight of the acyclic amine compound remains unreacted in the lubricant composition as a reference.

  In one embodiment, the percentage of acyclic amine compound that remains unreacted is determined after all of the components present in the lubricant composition have reached equilibrium with each other. The time required to reach equilibrium with the lubricant composition can vary widely. For example, the time required to reach equilibrium can range from 1 minute to several days or weeks. In certain embodiments, the percentage of acyclic amine compound that remains unreacted in the lubricant composition is 1 minute, 1 hour, 5 hours, 12 hours, 1 day, 2 days, 3 days, 1 week. Determined after 1 month, 6 months, or 1 year.

  In certain embodiments, the lubricant composition is less than 0.1%, less than 0.01%, less than 0.001%, or 0.0001% by weight, based on the total weight of the lubricant composition. Less than a compound that may react with an acyclic amine compound. In certain embodiments, the lubricant composition may include a total amount of acid, anhydride, triazole and / or oxide that is less than 0.1% by weight of the total weight of the lubricant composition. The term “acid” can include both traditional and Lewis acids. For example, acids include carboxylic acids such as glycolic acid, lactic acid and hydroacrylic acid; alkylated succinic acids; alkyl aromatic sulfonic acids; and fatty acids. Exemplary Lewis acids include alkyl aluminates; alkyl titanates; molybdenum compounds such as molybdenum thiocarbamate and molybdenum carbamate; and molybdenum sulfide. “Anhydrides” are exemplified by alkylated succinic anhydrides and acrylates. Triazoles are benzotriazole and derivatives thereof; toltriazole and derivatives thereof; 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, 4,4′-methylene-bis-benzotriazole, 4,5,6,7-tetrahydro -Represented by benzotriazole, salicylidenepropylenediamine, salicylamino-guanidine and its salts. Oxides can be represented by alkylene oxides such as ethylene oxide and propylene oxide; metal oxides; alkoxylated alcohols; alkoxylated amines; or alkoxylated esters. Alternatively, the lubricant composition may comprise a total amount of acid, anhydride, triazole that is less than 0.01% by weight, less than 0.001% by weight, or less than 0.0001% by weight, based on the total weight of the lubricant composition. And oxides. Alternatively or additionally, the lubricant composition may be free of acids, anhydrides, triazoles, and oxides.

  In yet another embodiment, the lubricant composition can consist of or consist essentially of a base oil and an acyclic amine compound. The lubricant composition may consist of or consist essentially of a base oil and an acyclic amine compound in addition to one or more additives that do not impair the functionality or performance of the acyclic amine compound. Conceivable. In various embodiments where the lubricant composition consists essentially of a base oil and an acyclic amine compound, the lubricant composition is less than 0.01% by weight, less than 0.001% by weight, or 0.0001% by weight. Contains less or less acid, anhydride, triazole, and oxide. In another embodiment, the term “consisting essentially of” describes that it does not include compounds that significantly affect the overall performance of the lubricant composition as recognized by those skilled in the art. . For example, a compound that significantly affects the overall performance of the lubricant composition may be described by a compound that adversely affects the lubricant composition's TBN boost, lubricity, seal compatibility, ability to inhibit corrosion, or acidity. .

  As described above, the acyclic amine compound improves the TBN of the lubricant composition. TBN is an industry standard measurement used to correlate the basicity of any material with the basicity of potassium hydroxide. This value is reported as mg KOH / g and is measured according to ASTM D4739 for each additive. The TBN value of the acyclic amine compound is at least 70 mg KOH, at least 100 mg KOH, or at least 150 mg KOH per gram of the acyclic amine compound.

  In one embodiment, the lubricant composition comprises an amine compound having a TBN (ASTM of at least 5%, at least 10%, at least 20%, at least 40%, at least 60%, at least 80%, or even 100% composition. D4739). Further, in certain embodiments, the lubricant composition comprises 0.5-15 mg KOH / g, 1-12 mg KOH / g, 0.5-4 mg KOH / g, 1-3 mg KOH / g TBN (ASTM In an amount that provides the lubricant composition (measured in accordance with D4739).

  The lubricant composition may have a TBN value of at least 1 mg KOH per gram of lubricant composition. Alternatively, the lubricant composition has a TBN value in the range of 1-15 mg KOH, 5-15 mg KOH, or 9-12 mg KOH per gram of lubricant composition when tested according to ASTM D2896.

  The acyclic amine compound is non-aggressive against the fluoroelastomer seal. Fluoroelastomer seals can be used in various applications such as o-rings, fuel seals, valve stem seals, rotating shaft seals, shaft seals, and engine seals. Fluoroelastomer seals can also be used in various industries such as the automotive, aviation, appliance, and chemical processing industries. Fluoroelastomers are classified under, for example, FKM under ASTM D1418 and ISO 1629. Fluoroelastomers include copolymers of hexafluoropropylene (HFP) and vinylidene fluoride (VDF or VF2), tetrafluoroethylene (TFE), terpolymers of vinylidene fluoride and hexafluoropropylene, perfluoromethyl vinyl ether (PMVE), Mention may be made of copolymers of TFE and propylene and copolymers of TFE, PMVE and ethylene. The fluorine content varies, for example, between 66 and 70% by weight based on the total weight of the fluoropolymer seal. FKM is a polymethylene type fluororubber having a fluoro substituent and a perfluoroalkyl or perfluoroalkoxy group on a polymer chain.

  The compatibility of the fluoroelastomer seal with the acyclic amine compound can be determined by the method defined in CEC-L-39-T96. In general, conventional amines are very detrimental to fluoroelastomer components. However, the amine compounds of the present invention show positive results for compatibility with fluoroelastomer seals.

  The CEC-L-39-T96 seal compatibility test involves dipping a seal or gasket in a lubricant composition, heating the lubricant composition to an elevated temperature with the seal contained therein, and increasing the This is carried out by maintaining the obtained temperature for a certain period of time. The seal is then removed and dried, and the mechanical properties of the seal are evaluated and compared to a seal specimen that was not heated in the lubricant composition. The percentage changes in these properties are analyzed to assess the compatibility of the seal with the lubricant composition. The introduction of an amine compound into the lubricant composition reduces the tendency to break the seal of the lubricant composition relative to other amine compounds.

  In certain embodiments, the base oil is selected from an API Group I base oil, an API Group II base oil, an API Group III base oil, an API Group IV base oil, an API Group V base oil, and combinations thereof. In one embodiment, the base oil includes an API Group II base oil.

  Base oils are classified according to the American Petroleum Institute (API) base oil compatibility guidelines. In other words, the base oil may be further described as comprising one or more of the five base oils: Group I (sulfur content greater than 0.03% by weight and / or less than 90% by weight Saturation, viscosity index 80-119); Group II (0.03% by mass or less sulfur content and 90% by mass or more saturation, viscosity index 80-119); Group III (0.03% by mass or less) Sulfur content and 90% by weight saturation or more, 119 or more viscosity index); Group IV (all polyalphaolefins (PAO)); and Group V (not included in Groups I, II, III, or IV) Everything else).

  Base oils typically have viscosities in the range of 1-20 cSt when tested according to ASTM D445 at 100 ° C. Alternatively, the base oil viscosity can range from 3 to 17 cSt, or from 5 to 14 cSt when tested according to ASTM D445 at 100 ° C.

  Base oils can further be defined as crankcase lubricants for spark-ignition and compression-ignited internal combustion engines, including automobile and truck engines, two-stroke engines, aircraft piston engines, and marine and railway diesel engines. Alternatively, base oil can be further defined as oil to be used in gas engines, stationary power engines, and turbines. Base oils can be further defined as heavy or light load engine oils.

In yet another embodiment, the base oil may further comprise one or more alkylene oxide polymers and interpolymers and derivatives thereof in which the terminal hydroxyl groups have been modified by esterification, etherification, or similar reactions. Can be defined as Typically, these synthetic oils are prepared by polymerizing ethylene oxide or propylene oxide to form a polyoxyalkylene polymer, which can be further reacted to form a synthetic oil. For example, alkyl and aryl ethers of these polyoxyalkylene polymers (eg, methyl polyisopropylene glycol ether having an average molecular weight of 1,000; diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1,000; and 1,000 to 1 , Diethyl ether of polypropylene glycol having a molecular weight of 500) and / or their mono- and polycarboxylic acid esters (eg acetate esters, mixed C _{3 to} C ₈ fatty acid esters, or C ₁₃ oxo acid diesters of tetraethylene glycol) Can also be utilized as a base oil.

  The lubricant composition may be a low SAPS oil containing less than 3%, less than 1%, or less than 0.5% by weight sulfated ash, based on the total weight of the lubricant composition.

  The base oil is typically 70-99.9%, 80-99.9%, 90-99.9%, or 85-95% by weight, based on the total weight of the lubricant composition. Present in the lubricant composition in amounts ranging from. Alternatively, the base oil is lubricated in an amount greater than 70% by weight, greater than 80% by weight, greater than 90% by weight, greater than 95% by weight, or greater than 99% by weight, based on the total weight of the lubricant composition. It can be present in the agent composition. In various embodiments, the amount of base oil (including diluent or carrier oil present) in the lubricant composition is 80-99.5% by weight, 85-85, based on the total weight of the lubricant composition. It is 96 mass% or 90-95 mass%.

  Alternatively, the base oil is present in the lubricant composition in an amount ranging from 0.1 to 50% by weight, 1 to 25% by weight, or 1 to 15% by weight, based on the total weight of the lubricant composition. obtain.

  The lubricant composition may further include one or more additives to improve various chemical and / or physical properties of the lubricant composition. Specific examples of one or more additives include antiwear additives, antioxidants, metal deactivators (or passivators), rust inhibitors, viscosity index improvers, pour point depressants, dispersants. , Detergents, and anti-friction additives. Each additive may be used alone or in combination. The additive, if used, can be used in various amounts. Lubricant compositions can be formulated with multiple auxiliary ingredients to achieve specific performance goals for use in a particular application. For example, the lubricant composition can be a rust and oxidation formulation, a hydraulic fluid formulation, a turbine oil, and an internal combustion engine formulation.

When used, the antiwear additive can be of various types. In one embodiment, the antiwear additive is a dihydrocarbyl-dithiophosphate, such as a zinc dialkyldithiophosphate. Dihydrocarbyl-dithiophosphate has the following general formula:
[R ⁴ O (R ⁵ O) PS (S)] ₂ M
(Wherein R ⁴ and R ⁵ are each independently a hydrocarbyl group having 1 to 20 carbon atoms, and M is a metal atom or an ammonium group)
Can be represented by: For example, R ⁴ and R ⁵ are each independently a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _3-20 cycloalkyl group, a C _1-20 aralkyl group, or a C _3-20 aryl group. The metal atom is selected from the group comprising aluminum, lead, tin, manganese, cobalt, nickel, or zinc. Ammonium groups can be derived from ammonia or primary, secondary or tertiary amines. The ammonium group has the formula R ⁶ R ⁷ R ⁸ R ⁹ N ⁺ , wherein R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently have a hydrogen atom or 1 to 150 carbon atoms. Which represents a hydrocarbyl group). In certain embodiments, R ⁶ , R ⁷ , R ⁸ , and R ⁹ can each independently represent a hydrocarbyl group having 4 to 30 carbon atoms.

  Alternatively, antiwear additives include sulfur, phosphorus, and / or halogen containing compounds such as sulfurized olefins and vegetable oils, alkylated triphenyl phosphates, tolyl phosphates, tricresyl phosphates, chlorinated paraffins, alkyl and aryl disulfides. -And trisulfides, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyltriazole, bis (2-ethylhexyl) aminomethyltolyltriazole, 2,5-dimercapto-1,3,4-thiadiazole Derivatives of ethyl 3-[(diisopropoxyphosphinothioyl) thio] propionate, triphenylthiophosphate (triphenylphosphorothioate), tris (alkylphenyl) phosphorothioe And mixtures thereof (eg, tris (isononylphenyl) phosphorothioate), diphenyl-monononylphenyl phosphorothioate, isobutylphenyl-diphenyl phosphorothioate, dodecylamine salt of 3-hydroxy-1,3-thiaphosphatane 3-oxide, trithiophosphate 5 , 5,5-tris [isooctyl 2-acetate], derivatives of 2-mercaptobenzothiazole, such as 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3- Benzothiazole, ethoxycarbonyl-5-octyldithiocarbamate, and / or combinations thereof.

  If used, the anti-wear additive can be used in various amounts. The anti-wear additive is typically 0.1-20%, 0.5-15%, 1-10%, 0.1-1 based on the total weight of the lubricant composition. It is present in the lubricant composition in an amount in the range of mass%, 0.1 to 0.5 mass%, or 0.1 to 1.5 mass%. Alternatively, the anti-wear additive is less than 20%, less than 10%, less than 5%, less than 1%, or less than 0.1% by weight based on the total weight of the lubricant composition. Can exist. The antiwear additives are each in an amount ranging from 0.1 to 99%, 1 to 70%, 5 to 50%, or 25 to 50% by weight, based on the total weight of the additive concentrate. It can be present in the additive concentrate.

  When used, the antioxidant can be of various types. Suitable antioxidants include alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert. -Butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4 -Methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylun Ca-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadeca-1′-yl) phenol, 2,4-dimethyl-6- (1′-methyltridec-1′-yl) ) Phenol, and combinations thereof.

  Further examples of suitable antioxidants include alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthio And methyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3, 5-Di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and combinations thereof may also be utilized.

  Furthermore, hydroxylated thiodiphenyl ethers such as 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6- tert-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-2-methylphenol), 4,4′-thiobis (3,6-di-sec-amylphenol), 4, 4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide, and combinations thereof can also be used.

  Further, alkylidene bisphenols such as 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), 2,2′- Methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol) 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (6-tert- Butyl-4-isobutylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol Nord], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5- Methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl- 4-hydroxy-2-methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3′-tert-butyl-4′- Hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3′-tert-butyl-2′-hydroxy-5′-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-tert-butyl -4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5 -Tert-butyl-4-hydroxy-2-methylphenyl) pentane, and combinations thereof, are also utilized in lubricant compositions as antioxidants. It is conceivable to obtain.

  O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl Benzyl mercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, bis (3 5-Di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate, and combinations thereof may also be utilized.

  Hydroxybenzylated malonates such as dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert-butyl-4- Hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3 , 3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, and combinations thereof are also suitable for use as antioxidants.

  Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4, 6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl- 4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl, 2 4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4 -Hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate, and combinations thereof may also be used.

  Further examples of antioxidants include aromatic hydroxybenzyl compounds such as 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethyl. Benzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di- tert-butyl-4-hydroxybenzyl) phenol, and combinations thereof. Benzyl phosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl 3,5-di-tert -Calcium salt of monoethyl ester of butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid , And combinations thereof may also be utilized. In addition, acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate may be utilized.

  [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9 -Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, With 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane Esters and so Combinations of al may also be used. Furthermore, β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane Este with , And it is considered that combinations thereof may be used.

  Further examples of suitable antioxidants include those containing nitrogen, such as amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N′-bis. (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine. Examples of other suitable antioxidants include amine-based antioxidants such as N, N′-diisopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N, N′-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N′-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N′-bis (1-methyl) Heptyl) -p-phenylenediamine, Ν, Ν′-dicyclohexyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N, N′-bis (2-naphthyl) -p-phenylenediamine, N -Isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl Ruheptyl) -N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N′-dimethyl-N, N ′ -Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example, p, p '-Di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4- Methoxypheni ) Amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4 , 4′-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ′, 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mono- and dialkylated tert-butyl / tert-octyldiphenylamine mixtures, mono- and dialkylated isopropyl / isohexyldiphenylamine mixtures Of mono- and dialkylated tert-butyldiphenylamine Compound, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine, N, N, N ′, N′-tetraphenyl-1,4-diaminobut-2 -Ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol, and combinations thereof.

  Further examples of suitable antioxidants include aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamic acid or dithiophosphoric acid, 2,2,12,12-tetramethyl -5,9-dihydroxy-3,7,1-trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane, and combinations thereof Is mentioned. In addition, sulfurized fatty acid esters, sulfurized fats and sulfurized olefins, and combinations thereof may be used.

  When used, the antioxidant can be used in various amounts. The antioxidant is typically in an amount ranging from 0.01 to 5%, 0.1 to 3%, or 0.5 to 2% by weight, based on the total weight of the lubricant composition. Present in the lubricant composition. Alternatively, the antioxidant may be present in an amount of less than 5% by weight, less than 3% by weight, or less than 2% by weight, based on the total weight of the lubricant composition. Antioxidants are additive concentrated in amounts ranging from 0.1 to 99%, 1 to 70%, 5 to 50%, or 25 to 50% by weight, based on the total weight of the additive concentrate. It can exist in things.

  If used, the metal deactivator may be of various types. Suitable metal deactivators include benzotriazole and its derivatives, such as 4 or 5-alkylbenzotriazole (eg, toltriazole) and its derivatives, 4,5,6,7-tetrahydrobenzotriazole and 5,5. '-Methylenebisbenzotriazole; Mannich bases of benzotriazole or toltriazole, such as 1- [bis (2-ethylhexyl) aminomethyl) toltriazole and 1- [bis (2-ethylhexyl) aminomethyl) benzotriazole; and alkoxy Alkylbenzotriazoles such as 1- (nonyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl) toltriazole and combinations thereof It is.

  Further examples of suitable metal deactivators include 1,2,4-triazole and its derivatives, such as 3-alkyl (or aryl) -1,2,4-triazole, and 1,2,4- Mannich base of triazole, such as 1- [bis (2-ethylhexyl) aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazole, such as 1- (1-butoxyethyl) -1 , 2,4-triazole; and acylated 3-amino-1,2,4-triazole, imidazole derivatives such as 4,4′-methylenebis (2-undecyl-5-methylimidazole) and bis [(N-methyl ) Imidazol-2-yl] carbinol octyl ether, and combinations thereof. Further examples of suitable metal deactivators include sulfur-containing heterocyclic compounds such as 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and its derivatives; and 3,5 -Bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one, and combinations thereof. Still further examples of metal deactivators include amino compounds such as salicylidenepropylenediamine, salicylaminoguanidine and salts thereof, and combinations thereof.

  If used, the metal deactivator can be used in various amounts. The metal deactivator is typically 0.01 to 0.1% by weight, 0.05 to 0.01% by weight, or 0.07 to 0.005%, based on the total weight of the lubricant composition. Present in the lubricant composition in an amount ranging from 1% by weight. Alternatively, the metal deactivator may be present in an amount of less than 0.1% by weight, less than 0.7% by weight, or less than 0.5% by weight, based on the total weight of the lubricant composition. The metal deactivator is in an amount ranging from 0.1% to 99%, 1 to 70%, 5 to 50%, or 25 to 50% by weight, based on the total weight of the additive concentrate. Can be present in the additive concentrate.

  When used, the rust inhibitor and / or friction modifier may be of various types. Suitable examples of rust inhibitors and / or friction modifiers include organic acids, their esters, metal salts, amine salts and anhydrides such as alkyl and alkenyl succinic acids and their alcohols, diols or hydroxycarboxylic acids. Partial esters, partial amides of alkyl and alkenyl succinic acids, 4-nonylphenoxyacetic acid, alkoxy and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and their amine salts, and also N-oleoyl Sarcosine, sorbitan monooleate, lead naphthenate, alkenyl succinic anhydrides such as dodecenyl succinic anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol and their amine salts, and combinations thereof . Further examples include nitrogen-containing compounds such as primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids such as oil-soluble alkyl ammonium carboxylates, Include 1- [N, N-bis (2-hydroxyethyl) amino] -3- (4-nonylphenoxy) propan-2-ol, and combinations thereof. Further examples include heterocyclic compounds such as substituted imidazolines and oxazolines, and 2-heptadecenyl-1- (2-hydroxyethyl) imidazoline, phosphorus-containing compounds such as phosphate partial esters or amines of phosphate partial esters Salts, and zinc dialkyldithiophosphates, molybdenum containing compounds such as molybdenum dithiocarbamate and other sulfur and phosphorus containing derivatives, sulfur containing compounds such as barium dinonyl naphthalene sulfonate, calcium petroleum sulfonate, alkylthio-substituted aliphatic carboxylic acids, Esters of aliphatic 2-sulfocarboxylic acids and salts thereof, glycerol derivatives such as glycerol monooleate, 1- (alkylphenoxy) -3- (2-hydroxyethyl) glycerol, 1- (alkylphenoxy) 3- (2,3-dihydroxypropyl) glycerol and 2-carboxyalkyl-1,3-dialkyl glycerol, and combinations thereof.

  When used, rust inhibitors and / or friction modifiers can be used in various amounts. The rust inhibitor and / or friction modifier is typically 0.01 to 0.1% by weight, 0.05 to 0.01% by weight, or 0.005%, based on the total weight of the lubricant composition. It is present in the lubricant composition in an amount ranging from 07 to 0.1% by weight. Alternatively, the rust inhibitor and / or friction modifier is present in an amount of less than 0.1% by weight, less than 0.7% by weight, or less than 0.5% by weight, based on the total weight of the lubricant composition. obtain. The rust inhibitor and / or friction modifier is 0.01 to 0.1 mass%, 0.05 to 0.01 mass%, or 0.07 to 0.1, based on the total mass of the additive concentrate. It can be present in the additive concentrate in an amount in the range of% by weight.

  If used, the viscosity index improver (VII) may be of various types. Suitable examples of VII include polyacrylates, polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidone, polybutenes, olefin copolymers, styrene / acrylate copolymers and polyethers, and combinations thereof. If used, VII can be used in various amounts. VII is typically present in the lubricant composition in an amount ranging from 0.01 to 20%, 1 to 15%, or 1 to 10% by weight, based on the total weight of the lubricant composition. To do. Alternatively, VII may be present in an amount less than 10%, less than 8%, or less than 5% by weight, based on the total weight of the lubricant composition. VII may be present in the additive concentrate in an amount ranging from 0.01 to 20%, 1 to 15%, or 1 to 10% by weight, based on the total weight of the additive concentrate.

  When used, the pour point depressant may be of various types. Suitable examples of pour point depressants include polymethacrylates and alkylated naphthalene derivatives, and combinations thereof.

  If used, the pour point depressant can be used in various amounts. The pour point depressant is typically 0.01-0.1 wt%, 0.05-0.01 wt%, or 0.07-0.1 wt%, based on the total weight of the lubricant composition. Present in the lubricant composition in an amount in the range of%. Alternatively, the pour point depressant may be present in an amount of less than 0.1 wt%, less than 0.7 wt%, or less than 0.5 wt%, based on the total weight of the lubricant composition. The pour point depressant is an additive in an amount ranging from 0.1 to 99%, 1 to 70%, 5 to 50%, or 25 to 50% by weight, based on the total weight of the additive concentrate. It can be present in the concentrate.

  If used, the dispersant may be of various types. Suitable examples of dispersants include polybutenyl succinic amides or imides, polybutenyl phosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and phenolates, succinic esters and alkylphenolamines (Mannich bases), and these The combination of is mentioned.

The amine dispersant may be a polyalkeneamine. The polyalkeneamine contains a polyalkene moiety. The polyalkene moiety is the polymerization product of the same or different linear or branched C _2-6 olefin monomers. Examples of suitable olefin monomers are ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methylbutene, 1-hexene, 2-methylpentene, 3-methylpentene, and 4-methylpentene. The polyalkene moiety has a number average molecular weight M _n in the range of 200 to 10,000.

In one configuration, the polyalkeneamine is derived from polyisobutene. Particularly suitable polyisobutenes are known as “highly reactive” polyisobutenes characterized by a high content of terminal double bonds. Suitable highly reactive polyisobutenes are, for example, greater than 70 mole%, greater than 80 mole%, greater than 85 mole%, greater than 90 mole%, or 92 moles based on the total number of double bonds in the polyisobutene Polyisobutene with a proportion of terminal vinylidene double bonds greater than%. Even more preferred are polyisobutenes, especially with a homogeneous polymer framework. A uniform polymer framework is a polyisobutene composed of at least 85%, 90%, or 95% by weight of isobutene units. Such highly reactive polyisobutene preferably has a number average molecular weight in the above range. Further, the highly reactive polyisobutene may have a polydispersity in the range of 1.05-7, or 1.1-2.5. The highly reactive polyisobutene may have a polydispersity of less than 1.9, or less than 1.5. Polydispersity means the quotient of the weight average molecular weight _Mw divided by the number average molecular weight _Mn .

  The polyalkeneamine may contain moieties derived from succinic anhydride and may contain hydroxyl groups and / or amino groups and / or amide groups and / or imide groups. For example, amine dispersants are polyisobutenyl succinates obtained by reaction via a thermal pathway with maleic anhydride or via conventional or highly reactive polyisobutene having a number average molecular weight in the range of 300-5000 or via chlorinated polyisobutene. It can be derived from an acid anhydride. Of particular interest are derivatives of aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.

  In order to produce a polyalkeneamine, the polyalkene component can be aminated in a manner known per se. A preferred process proceeds via the preparation of an oxo intermediate by hydroformylation followed by reductive amination in the presence of the appropriate nitrogen compound.

Is the amine dispersant represented by the general formula: HNR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ may each independently be a hydrogen atom or a hydrocarbyl group having 1 to 17 carbon atoms? Or analogs thereof that are mono- or polyhydroxylated. The amine dispersant may also be a poly (oxyalkyl) group or a general formula Z—NH— (C ₁ -C ₆ -alkylene-NH) _m —C ₁ -C ₆ alkylene, where m is in the range of 0-5. A polyalkylene polyamine of the integer, Z being a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms, wherein C ₁ -C ₆ alkylene represents the corresponding bridged analog of the alkyl group) Can be a group. The amine dispersant may also be a polyalkyleneimine group composed of _{1 to} 10 C ₁ -C ₄ alkyleneimine groups, or optionally with one to a nitrogen atom to which they are attached. a three C ₁ -C ₄ heterocyclic 5- to 7-membered optionally substituted with one further ring heteroatom such as substituted and optionally O or N with an alkyl group.

  Examples of suitable alkyl groups are linear or branched groups having 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl or n-propyl, n-, iso-, sec- or tert-butyl, n- or isopentyl; further n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl and n-octadecyl, as well as its mono- or multi-branched analogs; and corresponding groups in which the hydrocarbon chain has one or more ether bridges.

  Examples of suitable alkenyl groups include monounsaturated or polyunsaturated analogs of alkyl groups having 2 to 18 carbon atoms, where the double bond may be at any position in the hydrocarbon chain, preferably Includes monounsaturated or diunsaturated analogs.

Examples of C ₄ -C ₁₈ cycloalkyl group, cyclobutyl, cyclopentyl and cyclohexyl and their analogues substituted by one to three _C 1 -C ₄ alkyl _group: C 1 -C ₄ alkyl group Is for example selected from methyl, ethyl, iso- or n-propyl, n-, iso-, sec- or tert-butyl.

Examples of an arylalkyl group, C ₁ -C ₁₈ alkyl groups and monocyclic or bicyclic, 4-membered to 7-membered, especially 6-membered aromatic or heteroaromatic group, for example, phenyl, pyridyl, naphthyl And aryl groups derived from biphenyl.

Examples of suitable compounds of the general formula HNR ¹⁰ R ¹¹ are ammonia; primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine , pentylamine, hexylamine, cyclopentylamine and cyclohexylamine; following primary amine of the _{formula: CH 3 -O-C 2 H} 4 -NH 2, C 2 H 5 -O-C 2 H 4 -NH 2, _{CH 3 -O-C 3 H 6} -NH 2, C 2 H 5 -O-C 3 H 6 -NH 2, C 4 H 9 -O-C 4 H 8 -NH 2, HO-C 2 H 4 - _{NH 2, HO-C 3 H} 6 -NH 2 , and _{HO-C 4 H 8 -NH 2} ; secondary amines such as dimethylamine, diethylamine, methyl ethyl Ruamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine, dihexylamine, dicyclopentylamine, dicyclohexylamine and diphenylamine; Amine: (CH ₃ —O—C ₂ H ₄ ) ₂ NH, (C ₂ H ₅ —O—C ₂ H ₄ ) ₂ NH, (CH ₃ —O—C ₃ H ₆ ) ₂ NH, (C ₂ H _{5 -O-C 3 H 6)} 2 NH, (n-C 4 H 9 -O-C 4 H 8) 2 NH, (HO-C 2 H 4) 2 NH, (HO-C 3 H 6) 2 NH and _{(HO-C 4 H 8)} 2 NH; and heterocyclic amines, such as pyrrolidine, piperidine, morpholine and piperazine, further their substituted derivatives, for example , _{N-C 1 to 6} alkyl piperazine and dimethyl morpholine; and polyamines and polyimines, for example, n- propylene diamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, triethylenetetramine, and polyethyleneimine, further These alkylation products are, for example, 3- (dimethylamino) -n-propylamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine and N, N, N ′, N′-tetramethyldiethylenetriamine. .

  If used, the dispersant may be used in various amounts. The dispersant is typically 0.01 to 15%, 0.1 to 12%, 0.5 to 10%, or 1 to 8% by weight, based on the total weight of the lubricant composition. Present in the lubricant composition in amounts ranging from. Alternatively, the dispersant may be present in an amount less than 15%, less than 12%, less than 10%, less than 5%, or less than 1% by weight, based on the total weight of the lubricant composition. These dispersants are additives in amounts ranging from 0.1 to 99%, 1 to 70%, 5 to 50%, or 25 to 50% by weight, based on the total weight of the additive concentrate. It can be present in the concentrate.

  If used, the detergent may be of various types. Suitable examples of detergents include overbased or neutral metal sulfonates, phenates and salicylates, and combinations thereof.

  If used, the detergent may be used in various amounts. The detergent is typically 0.01-5%, 0.1-4%, 0.5-3%, or 1-3% by weight, based on the total weight of the lubricant composition. Present in the lubricant composition in amounts ranging from. Alternatively, the detergent may be present in an amount of less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% by weight, based on the total weight of the lubricant composition. The detergent is typically in an amount in the range of 0.1-99%, 1-70%, 5-50%, or 25-50% by weight, based on the total weight of the additive concentrate. Present in the additive concentrate.

  In various embodiments, the lubricant composition is substantially free of water, eg, the lubricant composition is less than 5% by weight, less than 1% by weight, 0%, based on the total weight of the lubricant composition. Less than 5% by weight or less than 0.1% by weight water. Alternatively, the lubricant composition may be completely free of water.

  Since some of the above compounds may interact in the lubricant composition, the components of the final form of the lubricant composition may differ from those components that were initially added or combined together. . Some products formed thereby are not easily described or described, including products formed when the lubricant composition of the present invention is used in its intended application. Nevertheless, all such modifications, reaction products, and products formed when using the lubricant composition of the present invention in its intended application are also clearly contemplated, thereby Included in the book. Various embodiments of the present invention include products formed from the use of one or more modifications, reaction products, and lubricant compositions as described above.

  A method of lubricating a system including a fluoropolymer seal is also provided. The method includes contacting the fluoropolymer seal with the acyclic amine compound described above. The acyclic amine compound may be dissolved in the base oil, and thus the method may include contacting the fluoropolymer seal with the lubricant composition. A system that includes a fluoropolymer seal may include an internal combustion engine. Alternatively, a system that includes a fluoropolymer seal may include devices where the lubricant composition is used, such as conveyors, transmissions, diesel engines, gearing, pulleys, and other machines.

  Furthermore, a method for forming a lubricant composition is provided. The method includes combining a base oil and the acyclic amine compound described above. Thus, the amine compound can be added directly to the base oil by dispersing or dissolving it in the base oil at the desired level of concentration. Alternatively, the base oil can be added directly to the amine compound with stirring until the amine compound is provided at the desired level of concentration. Such blending can occur at ambient or elevated temperatures. In one embodiment, one or more additives are blended into the concentrate, which is then blended into the base oil to make a lubricant composition. The concentrate is typically formulated to give the desired concentration in the lubricant composition when the concentrate is combined with a predetermined amount of base oil.

  A fully formulated lubricant composition containing a dispersant, detergent, amine antioxidant, phenolic antioxidant, antifoam, base oil, antiwear additive, pour point depressant and viscosity modifier was prepared. . This lubricant composition is a typical commercial crankcase lubricant, referred to as a “reference lubricant” and used as a baseline to compare the effect of different amine compounds on seal compatibility. .

  Reference lubricants were combined with a variety of different amine compounds to determine the effect of amine compounds on seal compatibility. Example # 1 of the present invention includes an amine compound of the present invention according to one embodiment. Comparative Examples # 1-3 include other amine compounds that are outside the scope of the present invention.

  The compound added to the reference lubricant in Example # 1 of the present invention is tert-amyl-tert-butylamine. The compound added to the reference lubricant in Comparative Example # 1 is 1-dodecylamine; the compound added to the reference lubricant in Comparative Example # 2 is N, N-dimethylcyclohexylamine; and Comparative Example # The compound added to the reference lubricant in 3 is 4-benzylpiperidine.

  Each amine-based additive was added in an amount sufficient to provide 3 units of TBN relative to the reference lubricant TBN. The TBN of each of the obtained samples was measured according to ASTM D4739 and ASTM D2896, respectively (unit: mg KOH / g). An additional amount of base oil was added to each sample to give a comparable total mass. The amounts of the reference lubricant and added compounds for each of the inventive examples and comparative examples are shown in Table 1 below.

  The seal compatibility of the examples of the present invention and comparative examples was evaluated using the industry standard CEC L-39-T96 seal compatibility test. The CEC-L-39-T96 seal compatibility test is enhanced by dipping the seal or gasket in the lubricant composition and heating the lubricant composition to an elevated temperature with the seal contained therein. For a certain period of time. The seal is then removed and dried, and the mechanical properties of the seal are evaluated and compared to a seal specimen that was not heated in the lubricant composition. The percentage change in these properties is analyzed to assess the compatibility of the seal with the lubricant composition. Each formulation was tested twice under the same conditions (experiment # 1 and experiment # 2). The results of the seal compatibility test are shown in Table 2 and Table 3 below.

  As shown in Tables 2 and 3, the seal compatibility of Example # 1 of the present invention was improved with respect to tensile strength and elongation at break compared to the seal compatibility of Comparative Examples # 1-3. More specifically, the tensile strength of Example # 1 of the present invention is -44% and -49%, while the tensile strengths of Comparative Examples # 1, 2, and 3 are -64% and -70%, respectively; -75% and -75% and -70% and -69%. Similarly, the elongation at break of Example # 1 of the present invention was −67% and −71%, while the elongation at break of Comparative Examples # 1, 2, and 3 were −100% and −98, respectively. %; -82% and -78% and -75% and -76%.

  This test shows that the compositions of Comparative Examples # 1-3 reduced the tensile strength and elongation at break of the fluoroelastomer seal to a much greater degree than the compositions of Example # 1 of the present invention.

  Each TBN of the amine compound (invention and comparison) was measured according to ASTM D4739 (unit: mg KOH / g). The results are shown in Table 4 below.

  As shown in Tables 2-4, Example # 1 of the present invention showed a median TBN value relative to the TBN values of Comparative Examples # 1-3, but the seal fit of Example # 1 of the present invention. The properties were greatly improved with respect to tensile strength and elongation at break.

  The accompanying claims are not limited to the expressions and specific compounds, compositions, or methods described in the detailed description, and these vary between the specific embodiments falling within the scope of the appended claims. It should be understood that this is possible. For any Markush group considered herein to describe particular features or aspects of the various embodiments, the various special and / or unexpected results are independent of all other Markush elements. It should be understood that it can be obtained from each element of each Markush group. Each element of the Markush group may be considered individually and / or in combination with particular embodiments within the scope of the appended claims to provide adequate support.

  All ranges and sub-ranges that are considered when describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and such values are expressly set forth herein. It should also be understood that all ranges are described and contemplated, including integer values and / or decimal values therein, even if not. Those skilled in the art will readily understand that the enumerated ranges and subranges fully describe and enable various embodiments of the invention, and such ranges and subranges are related to the related half, I understand that it can be further drawn to a quarter, a quarter, a fifth, etc. By way of example only, the “0.1-0.9” range is the lower third, ie 0.1-0.3, the middle third, ie 0.4-0.6, and May be further drawn to the upper third, i.e. 0.7-0.9, which are individually and collectively within the scope of the appended claims, individually and / or collectively It provides good support for certain embodiments that are well and within the scope of the appended claims.

  Further, for terms that define or modify ranges such as “at least”, “greater”, “less than”, “below”, it should be understood that such terms include subranges and / or upper or lower limits. . As another example, a range of “at least 10” essentially includes subranges, such as at least 10-35 subranges, at least 10-25 subranges, 25-35 subranges, each subrange being Which may be considered individually and / or collectively and provide appropriate support for specific embodiments within the scope of the appended claims. Finally, individual numbers within the disclosed ranges may be considered and provide an appropriate basis for specific embodiments within the scope of the appended claims. For example, the range “from 1 to 9” includes various individual integers, such as 3, and individual numbers including a decimal point (or fraction), such as 4.1, which may be considered and attached Appropriate support is provided for specific embodiments within the scope of the claims.

  It should be understood that the present invention has been described by way of example, and that the terminology used is intended to be within the scope of the words of description rather than limitation. Many modifications and variations of the present invention are possible in light of the above teachings, and the invention may be practiced otherwise than as specifically described.

（式中、Ｒ^１はそれぞれ独立して水素及び１〜１７個の炭素原子を有するアルキル基から選択され、Ｒ^１のうち少なくとも２つは独立して選択されたアルキル基であり、
Ｒ^２はそれぞれ独立してアルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有し、且つ
Ｒ^３は水素及びアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有する）
を有する、前記クランクケース潤滑剤組成物。
３． 前記非環式アミン化合物が非重合体であり且つ１００〜１２００の範囲の質量平均分子量を有する、前記態様に記載の潤滑剤組成物。
４． 前記非環式アミン化合物が２００〜８００の範囲の質量平均分子量を有する、前記態様のいずれかに記載の潤滑剤組成物。
５． Ｒ^１がそれぞれ独立して選択された１〜８個の炭素原子を有するアルキル基である、前記態様のいずれかに記載の潤滑剤組成物。
６． Ｒ^２がそれぞれ独立して選択された１〜８個の炭素原子を有するアルキル基である、前記態様のいずれかに記載の潤滑剤組成物。
７． Ｒ^３が１〜４個の炭素原子を有するアルキル基である、前記態様のいずれかに記載の潤滑剤組成物。
８． 前記非環式アミン化合物が、ＡＳＴＭ Ｄ４７３９に従って試験される時に、前記非環式アミン化合物のグラム当たり少なくとも７０ｍｇ ＫＯＨのＴＢＮ値を有する、前記態様のいずれかに記載の潤滑剤組成物。
９． 前記潤滑剤組成物の全質量を基準として０．１質量％未満の、前記非環式アミン化合物と反応する化合物を含む、前記態様のいずれかに記載の潤滑剤組成物。
１０． 前記基油が、ＡＰＩ群Ｉ油、ＡＰＩ群ＩＩ油、ＡＰＩ群ＩＩＩ油、ＡＰＩ群ＩＶ油及びそれらの組み合わせから選択され、前記基油がＡＳＴＭ Ｄ４４５に従って１００℃で試験される時に１〜２０ｃＳｔの範囲の粘度を有する、前記態様のいずれかに記載の潤滑剤組成物。
１１． 前記潤滑剤組成物中での任意の反応前に前記潤滑剤組成物を形成するために使用される前記非環式アミン化合物の全質量を基準として、少なくとも９０質量％の前記非環式アミン化合物が、前記潤滑剤組成物において未反応のままである、前記態様のいずれかに記載の潤滑剤組成物。
１２． 基油と、クランクケース潤滑剤組成物の全質量を基準として０．１〜１０質量％の範囲の量で存在する非環式アミン化合物を含むクランクケース潤滑剤組成物による、フルオロポリマーシールを含むシステムの潤滑方法であって、前記方法が、
フルオロポリマーシールとクランクケース潤滑剤組成物とを接触させることを含み、
その際、非環式アミン化合物が以下の式（Ｉ）：

（式中、Ｒ^１はそれぞれ独立して水素及び１〜１７個の炭素原子を有するアルキル基から選択され、ここでＲ^１のうち少なくとも２つが独立して選択されたアルキル基であり、
Ｒ^２はそれぞれ独立してアルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有し、且つ
Ｒ^３は水素及びアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜１７個の炭素原子を有する）
を有する、前記方法。
１３． クランクケース潤滑剤組成物用の添加剤濃縮物であって、
硫黄及び／又はリンを含む耐摩耗性添加剤；及び
前記添加剤濃縮物の全質量を基準として、０．５〜９０質量％の範囲の量で存在する非環式アミン化合物を含み、前記非環式アミン化合物が以下の式（Ｉ）：

（式中、Ｒ^１はそれぞれ独立して水素及び１〜６個の炭素原子を有するアルキル基から選択され、ここでＲ^１のうち少なくとも２つは独立して選択されたアルキル基であり、
Ｒ^２はそれぞれ独立してアルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜６個の炭素原子を有し、且つ
Ｒ^３は水素及びアルコール基、アルキル基、アミド基、エーテル基、及びエステル基から選択され、それぞれ１〜４個の炭素原子を有する）
を有する、前記添加剤濃縮物。
１４． 前記非環式アミン化合物が非重合体であり且つ１００〜１２００の範囲の質量平均分子量を有する、前記態様１３に記載の添加剤濃縮物。
１５． 分散剤を更に含む、前記態様１３又は１４に記載の添加剤濃縮物。 Preferred embodiments of the present invention are as follows:
1. A crankcase lubricant composition comprising:
A base oil; and an acyclic amine compound present in an amount ranging from 0.1 to 10% by weight, based on the total weight of the crankcase lubricant composition, wherein the acyclic amine compound has the formula ( I)

Wherein each R ¹ is independently selected from hydrogen and an alkyl group having 1 to 17 carbon atoms, at least two of R ¹ are independently selected alkyl groups;
R ² is independently selected from an alkyl group, an amide group, an ether group, and an ester group, each having 1 to 17 carbon atoms, and R ³ is a hydrogen and alcohol group, an alkyl group, an amide group, Selected from ether and ester groups, each having 1 to 17 carbon atoms)
The crankcase lubricant composition comprising:
3. The lubricant composition according to the above embodiment, wherein the acyclic amine compound is a non-polymer and has a mass average molecular weight in the range of 100 to 1200.
4). The lubricant composition according to any of the preceding embodiments, wherein the acyclic amine compound has a weight average molecular weight in the range of 200-800.
5. The lubricant composition according to any of the preceding embodiments, wherein R ¹ is an independently selected alkyl group having 1 to 8 carbon atoms.
6). The lubricant composition according to any of the preceding embodiments, wherein R ² is an independently selected alkyl group having 1 to 8 carbon atoms.
7). The lubricant composition according to any of the preceding embodiments, wherein R ³ is an alkyl group having 1 to 4 carbon atoms.
8). The lubricant composition according to any of the preceding embodiments, wherein the acyclic amine compound has a TBN value of at least 70 mg KOH per gram of the acyclic amine compound when tested according to ASTM D4739.
9. The lubricant composition according to any of the preceding embodiments, comprising less than 0.1% by weight of a compound that reacts with the acyclic amine compound, based on the total weight of the lubricant composition.
10. 1-20 cSt when the base oil is selected from API Group I oil, API Group II oil, API Group III oil, API Group IV oil and combinations thereof, and the base oil is tested at 100 ° C. according to ASTM D445. The lubricant composition according to any of the preceding embodiments, having a viscosity in the range.
11. At least 90% by weight of the acyclic amine compound based on the total weight of the acyclic amine compound used to form the lubricant composition prior to any reaction in the lubricant composition. The lubricant composition according to any of the preceding embodiments, wherein remains unreacted in the lubricant composition.
12 Including a fluoropolymer seal with a base oil and a crankcase lubricant composition comprising an acyclic amine compound present in an amount ranging from 0.1 to 10 weight percent based on the total weight of the crankcase lubricant composition A system lubrication method comprising:
Contacting the fluoropolymer seal with the crankcase lubricant composition;
In that case, the acyclic amine compound is represented by the following formula (I):

Wherein each R ¹ is independently selected from hydrogen and an alkyl group having 1 to 17 carbon atoms, wherein at least two of R ¹ are independently selected alkyl groups;
R ² is independently selected from an alkyl group, an amide group, an ether group, and an ester group, each having 1 to 17 carbon atoms, and R ³ is a hydrogen and alcohol group, an alkyl group, an amide group, Selected from ether and ester groups, each having 1 to 17 carbon atoms)
Said method.
13. An additive concentrate for a crankcase lubricant composition comprising:
An antiwear additive comprising sulfur and / or phosphorus; and an acyclic amine compound present in an amount ranging from 0.5 to 90% by weight, based on the total weight of the additive concentrate, Cyclic amine compounds are represented by the following formula (I):

Wherein each R ¹ is independently selected from hydrogen and an alkyl group having 1 to 6 carbon atoms, wherein at least two of R ¹ are independently selected alkyl groups;
R ² is independently selected from an alkyl group, an amide group, an ether group, and an ester group, each having 1 to 6 carbon atoms, and R ³ is a hydrogen and alcohol group, an alkyl group, an amide group, Selected from ether and ester groups, each having 1 to 4 carbon atoms)
Said additive concentrate.
14 14. The additive concentrate according to embodiment 13, wherein the acyclic amine compound is non-polymeric and has a weight average molecular weight in the range of 100 to 1200.
15. The additive concentrate according to embodiment 13 or 14, further comprising a dispersant.

Claims (9)

A crankcase lubricant composition comprising:
A base oil; and an acyclic amine compound present in an amount ranging from 0.1 to 10% by weight, based on the total weight of the crankcase lubricant composition, wherein the acyclic amine compound has the formula ( I)

Wherein R ¹ is independently selected from alkyl groups having 1 to 8 carbon atoms,
Each R ² is independently selected from alkyl groups having 1 to 8 carbon atoms, and R ³ is selected from hydrogen and alcohol groups, alkyl groups, amide groups, ether groups, and ester groups; , Alkyl groups, amide groups, ether groups, and ester groups each have 1 to 17 carbon atoms)
And at least 90% by weight of the non-cyclic amine compound based on the total weight of the acyclic amine compound used to form the lubricant composition prior to any reaction in the lubricant composition. The crankcase lubricant composition, wherein the cyclic amine compound remains unreacted in the lubricant composition.   The crankcase lubricant composition of claim 1, wherein the acyclic amine compound is non-polymeric and has a weight average molecular weight in the range of 100-1200. R ³ is an alkyl group having 1 to 4 carbon atoms, a crankcase lubricant composition according to claim 1 or 2.   Crankcase according to any one of claims 1 to 3, wherein the acyclic amine compound has a TBN value of at least 70 mg KOH per gram of the acyclic amine compound when tested according to ASTM D4739. Lubricant composition.   The crankcase lubricant according to any one of claims 1 to 4, comprising less than 0.1% by mass of a compound that reacts with the acyclic amine compound based on the total mass of the lubricant composition. Composition.   1-20 cSt when the base oil is selected from API Group I oil, API Group II oil, API Group III oil, API Group IV oil and combinations thereof, and the base oil is tested at 100 ° C. according to ASTM D445. Crankcase lubricant composition according to any one of claims 1 to 5, having a viscosity in the range. Including a fluoropolymer seal with a base oil and a crankcase lubricant composition comprising an acyclic amine compound present in an amount ranging from 0.1 to 10 weight percent based on the total weight of the crankcase lubricant composition A system lubrication method comprising:
Contacting the fluoropolymer seal with the crankcase lubricant composition;
In that case, the acyclic amine compound is represented by the following formula (I):

Wherein R ¹ is independently selected from alkyl groups having 1 to 8 carbon atoms,
Each R ² is independently selected from alkyl groups having 1 to 8 carbon atoms, and R ³ is selected from hydrogen and alcohol groups, alkyl groups, amide groups, ether groups, and ester groups; , Alkyl groups, amide groups, ether groups, and ester groups each have 1 to 17 carbon atoms)
Said method. An additive concentrate for a crankcase lubricant composition comprising:
An antiwear additive comprising sulfur and / or phosphorus; and an acyclic amine compound present in an amount ranging from 0.5 to 90% by weight, based on the total weight of the additive concentrate, Cyclic amine compounds are represented by the following formula (I):

Wherein R ¹ is independently selected from alkyl groups having 1 to 8 carbon atoms,
Each R ² is independently selected from alkyl groups having 1 to 8 carbon atoms, and R ³ is selected from hydrogen and alcohol groups, alkyl groups, amide groups, ether groups, and ester groups; , Alkyl groups, amide groups, ether groups, and ester groups each have 1 to 4 carbon atoms)
Said additive concentrate.   The additive concentrate of claim 8, further comprising a dispersant.